US8133928B2 - Method for decanting preconditioned ion-exchange resin suspensions - Google Patents

Method for decanting preconditioned ion-exchange resin suspensions Download PDF

Info

Publication number
US8133928B2
US8133928B2 US12/129,851 US12985108A US8133928B2 US 8133928 B2 US8133928 B2 US 8133928B2 US 12985108 A US12985108 A US 12985108A US 8133928 B2 US8133928 B2 US 8133928B2
Authority
US
United States
Prior art keywords
ion
exchange resin
resin suspension
container
preconditioned
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US12/129,851
Other languages
English (en)
Other versions
US20080306174A1 (en
Inventor
Ernst-Joachim Alps
Ulrich Blaschke
Christian Münnich
Stefan Westernacher
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Assigned to BAYER MATERIALSCIENCE AG reassignment BAYER MATERIALSCIENCE AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BLASCHKE, ULRICH, MUENNICH, CHRISTIAN, ALPS, ERNST-JOACHIM, WESTERNACHER, STEFAN
Publication of US20080306174A1 publication Critical patent/US20080306174A1/en
Application granted granted Critical
Publication of US8133928B2 publication Critical patent/US8133928B2/en
Expired - Fee Related legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus

Definitions

  • German Patent Application No. 10 2007 026549 filed Jun. 8, 2007.
  • German Patent Application No. 10 2007 026549 and the references cited therein are incorporated by reference in their entirety for all useful purposes.
  • the field of the present invention relates to a method for the storage of pretreated, conditioned ion-exchange resin suspensions as catalysts for chemical reactions, and also relates to the storage, transportation and the decanting of these preconditioned ion-exchange resin suspensions into a reactor.
  • acid cation exchangers for the catalysis of chemical reactions, such as for example for the condensation of ketones or aldehydes with phenols to form bisphenols.
  • Condensation reactions are known in the literature, such as for example the synthesis of bisphenols, which is generally carried out by acid-catalyzed reaction of phenols with carbonyl compounds. This last reaction is generally carried out under heterogeneous catalysis in fixed bed or fluidized bed reactors, as well as in reactive columns.
  • Catalysts of cross-linked sulfonated polystyrene resins (acid ion-exchangers; cation exchangers) are normally used for example in the synthesis of bisphenols.
  • ion exchangers can optionally be chemically modified by covalently or ionically bound co-catalysts and are macroporous or in gel form, as is described in U.S. Pat. No. 4,191,843 and U.S. Pat. No. 3,037,052.
  • JP-A 000006296871 now describes methods by which the handling, storage and transportation of the unstable catalyst can be avoided. The methods outlined here describe how the conditioning takes place in the reactor subsequently used for the catalysis. JP-A 000006296871 thus describes a method in which the conditioning takes place beforehand in the reactor used for the catalysis, so that a storage and a transportation of the unstable ion exchanger is not necessary, but the reactor for the actual catalysis cannot simultaneously be used at the time of the conditioning.
  • a treatment of the ion exchanger that is carried out under stationary conditions, for example in a reaction apparatus, is likewise described in EP-A 1239958.
  • the implementation of a pre-treatment/conditioning of ion exchangers in the reaction apparatus has the disadvantage that the reaction apparatus during the conditioning is not available for the production process and the catalyst conditioning thus means a production breakdown.
  • WO-A 01/37992 The preconditioning of a cation-exchange resin suspension for the catalyzed reaction of acetone with phenol to form bisphenol A is described in WO-A 01/37992.
  • WO-A 01/37992 also describes how this preconditioning can be carried out in an external vessel upstream of the reactor, but does not describe how such a preconditioned ion-exchange resin suspension can be stored for a prolonged period or transported to other production sites and transferred there to the respective reactor, without the preconditioned ion-exchange resin suspension losing its properties that are important for the catalysis.
  • Such a procedure means a restriction as regards the efficient provision, arrangement and utilization of apparatuses and parts of equipment for the catalyst pre-treatment and conditioning, in particular for users operating a plurality of production plants in which a repeated catalyst exchange is necessary.
  • the object of the invention is accordingly to provide a process that enables the preconditioned ion-exchange resin suspension to be stored and also transported over prolonged periods and then decanted into a reactor, without the ion-exchanger losing over this time the necessary properties as a reaction catalyst.
  • the preconditioned ion-exchange resin suspension is independent of the production site, for example of the bisphenol synthesis, contrary to the teaching of JP-A 000006296871 and JP-A 000006304479.
  • the present invention is directed toward a process for the storage of pretreated, conditioned ion exchangers as catalysts for chemical reactions.
  • the preconditioned ion-exchange resin is kept as preconditioned ion-exchange resin suspension in a laboratory or transporting container and is either transported to a storage site and stored there temporarily, or is transported to a reactor to be filled and is transferred to the latter.
  • the process may be advantageous if the storage or transporting container can be heated.
  • the process may be advantageous if the ion-exchange resin suspension is kept in the storage or transporting container in the presence of less than 500 vol. ppm of oxygen in the gaseous phase with a solids content of 20 to 80 vol. % referred to the ion-exchange resin suspension.
  • the process may be advantageous if the preconditioned ion-exchange resin suspension present in the heatable storage or transporting container in liquid or solidified or partly solidified form is converted into a pumpable ion-exchange resin suspension by careful melting if the suspension is solidified or partially solidified, with less than 500 vol. ppm of oxygen in the gaseous phase, using suitable pumps that do not damage the ion exchanger, removed from the storage or transporting container and transferred via suitable pipelines or suitable flexible connections to a reactor at temperatures from 50° to 80° C. and with a solids content of 20 to 80 vol. % referred to the ion-exchange resin suspension, with less than 500 vol. ppm of oxygen in the gaseous phase.
  • the process may be advantageous if the liquid phase of the preconditioned ion-exchange resin suspension is an OH component.
  • the process may be advantageous if the OH component is phenol.
  • the process may be advantageous if the OH component is phenol that still contains a residual water content in the range from 0.1-10%, preferably 0.2-5%, particularly preferably 0.5-3%, referred to phenol.
  • the process may be advantageous if the ion exchangers of the preconditioned ion-exchange resin suspensions have a gel-type or macroporous structure.
  • the process may be advantageous if the liquid phase contained in the preconditioned ion-exchange resin suspension is, in the transfer from the storage or transporting container to the reactor, partly recycled in the circulation of the storage or transporting container ( 1 ) via the line ( 3 ), and partly recycled through the line ( 4 ) to the storage or transporting container ( 1 ).
  • the process may be advantageous if the preconditioned ion exchanger is stored in phenol and the amount of phenol referred to the total amount of the ion exchanger/phenol suspension is 20 to 80 wt. %.
  • the amount of liquid and solid phase in the ion exchanger/phenol suspension can vary during the conveying processes.
  • the process may be advantageous if the ion-exchange resin in the preconditioned ion-exchange resin suspension is a cationic ion-exchange resin.
  • the preconditioned ion-exchange resin suspension as end product of the catalyst pre-treatment and conditioning is transferred from the unit for the catalyst pretreatment with an oxygen content in the gaseous phase of less than 500 vol. ppm as ion-exchange resin suspension in a pumpable form to a storage or transporting container.
  • Suitable storage or transporting containers are those that allow the ion-exchange resin suspension to be in a pumpable form when it is removed, and are preferably heatable storage containers or transporting containers that consist of a suitable stainless steel or other materials that are corrosion resistant under storage conditions of the suspension or that are treated so as to be corrosion resistant.
  • Suitable materials for the storage or transporting containers are for example stainless steels of the types 1.4571, 1.4404 or other, enameled containers, ceramic or vitreous containers or plastics containers that are resistant to organic or inorganic acids or bases, water or atmospheric oxygen.
  • Suitable storage or transporting containers are for example heatable railway wagons, overseas containers or road tankers.
  • Stainless steel that is corrosion resistant under the storage and transporting conditions of the suspension is preferably used as container material.
  • Suitable containers preferably have ventilation and pressure release devices covered with a blanket of inert gas.
  • the preferred storage temperature is ⁇ 60° C., particularly preferably ⁇ 40° C.
  • the storage time is preferably less than 12 months, more preferably less than 6 months and most particularly preferably less than 3 months. If storage is for more than 12 months, then depending on the ion exchanger an additional operating step may be necessary in order to remove from the ion exchanger elutable amounts of acid that have possibly formed during the storage time.
  • Ion-exchange resin suspensions in pumpable form are understood to mean those ion-exchange resin suspensions that for the transfer with the aid of a pump have a temperature in the storage or transporting container that is in the range from 50° to 90° C., preferably 60° to 80° C., and that preferably have a solids content of 20 to 80 wt. %, more preferably 30 to 70 wt. %.
  • the preconditioned ion-exchange resin suspension can be present in liquid, solidified or partially solidified form in the storage or transporting container during the storage or transportation with less than 500 vol. ppm of oxygen.
  • the preconditioned ion-exchange resin suspension is transferred to a reactor after the storage time has elapsed or after completion of the transportation, wherein the preconditioned ion-exchange resin suspension, should it not be in pumpable form but instead in solidified or partially solidified form, is carefully melted and the preconditioned ion-exchange resin suspension thus present in pumpable form is then transferred with suitable pumps from the storage or transporting container to the reactor with less than 500 vol. ppm of oxygen in the gaseous phase.
  • the pumps used for the transfer are those that do not damage the ion-exchange resin suspension, and are preferably those in which the conveyance takes place under low shear forces, low abrasion and thus in a gentle manner for the ion-exchange resin of the ion-exchange resin suspension, membrane pumps being particularly preferred.
  • the energy input in the conveyance of the ion-exchange resin suspensions should preferably not exceed 150 W/m 3 , and is preferably in the range from 20 to 130 W/m 3 .
  • pipes or suitable flexible connections are employed, which are corrosion resistant and can withstand unchanged the prevailing temperatures, which are in the range from 50° to 90° C. These pipes or flexible connections are preferably made of suitable materials, for example stainless steels of the types 1.4571, 1.4404 or other steels or steel flex hoses or reinforced hoses.
  • ion-exchange resin suspensions preconditioned by the disclosed process can be stored and transported in suitable liquids without being damaged by the mechanical stresses caused by the transportation, due to pumping and solidification as well as melting of the suspension.
  • conventional analytical techniques such as for example optical methods for determining particle fracture, microscopy and particle size measurements
  • the disclosed process which also includes the solidification, partial solidification and melting of the ion-exchange resin suspension, does not cause any measurable mechanical damage to the preconditioned ion exchanger.
  • Preconditioned ion-exchange resin suspensions can, being liquid phases, employ all those solvents that during the actual catalysis are not deleterious for the reaction and do not lead to superfluous by-products.
  • Preconditioned ion-exchange resin suspensions that are to be used subsequently as catalyst for the production of bisphenol can contain as liquid phases in the ion-exchange resin suspensions OH-containing liquid phases such as water and also organic solvents such as phenol or mixtures of these liquid phases. Phenol is preferred as liquid phase for the preconditioned ion-exchange resin suspensions that are to be used for the production of bisphenol A.
  • a preferred embodiment of the process is the storage or transportation of preconditioned ion-exchange resin suspensions that are to be used for the production of bisphenol A from acetone and phenol.
  • These preconditioned ion-exchange resin suspensions preferably contain an OH-containing liquid phase, particularly preferably phenol, as liquid phase in the ion-exchange resin suspension.
  • the ion exchanger conditioned in this way is outstandingly suitable for the production of bisphenols, in particular for the production of bisphenol A (BPA) from acetone and phenol.
  • BPA bisphenol A
  • the SPA produced with this ion exchanger has high product qualities and is particularly suitable for the production of polymers such as epoxy resins, and especially polycarbonates.
  • the polycarbonates thereby produced are used for the production of moulded articles, such as in particular compact discs, lenses and disks.
  • FIG. 1 illustrates the decanting of the preconditioned ion-exchange resin suspension.
  • reference numeral ( 1 ) denotes a storage or transporting container that can be heated
  • reference numeral ( 2 ) denotes a container that can be stirred and heated
  • reference numeral ( 3 ) denotes a line through which the ion-exchange resin suspension is conveyed to the container ( 2 )
  • reference numeral ( 4 ) denotes a line which diverts the liquid phase of the ion-exchange resin suspension
  • reference numeral ( 5 ) denotes a connection to a waste air venting device.
  • the ion-exchange resin suspension is conveyed by means of suitable conveying devices through the line ( 3 ) from the storage or transporting container ( 1 ) to the container ( 2 ).
  • suitable conveying devices are for example membrane pumps.
  • the gas volume of the container ( 2 ) which is preferably rendered inert, is displaced through the line ( 5 ).
  • Excess liquid phase of the ion-exchange resin suspension is recycled to the storage or transporting container ( 1 ) by means of suitable conveying devices via the line ( 4 ), which is provided with a filtration device in order to retain ion exchanger contained in the suspension.
  • Suitable measurement devices include measurement methods known to the person skilled in the art for measuring levels or conveyance of substance flows. All lines are preferably provided with heating means and equipped with safety devices against excess pressure.
  • a further advantage of the described process is the fact that, due to the process for the decanting and subsequent damage-free transportation of the preconditioned ion-exchange resin suspension, the utilization of a corresponding preconditioning unit independent of the actual catalysis reactor can be significantly increased by the dispatch and conveyance of the preconditioned ion-exchange resin suspension.
  • economic advantages are achieved in the operation of the preconditioning unit and on the other hand resources are conserved, since not each individual production plant has to be equipped with a preconditioning unit in order to utilize the advantage of the short downtime of a catalyst reactor during the preconditioning.
  • the phenol from the preconditioned ion-exchange resin suspension may after transportation, solidification and remelting, according to the disclosed process, be contaminated with acidic soluble fractions from the ion exchanger.
  • the amount of acid-containing elutable fractions in the thereby occurring phenol increases with the time that elapses between the conditioning and use in a reaction vessel.
  • the thereby occurring phenol is therefore preferably purified by distillation, in which connection the bottom of the column can be charged with up to 5 wt. % of a basic compound which is capable of retaining acidic constituents.
  • a preferred basic compound is sodium hydroxide.
  • the disclosed process for the conveyance, storage and transportation of ion-exchange resin suspensions is also suitable for the conveyance, storage and transportation of other dimensionally stable heterogeneous catalysts that can be used for example for condensation reactions.
  • the disclosed process avoids not only the disadvantages of the known stationary catalyst conditionings described above, but also permits at the same time the optimal use of the preconditioned ion-exchange resin suspensions as catalyst resins in condensation reactions, preferably in condensation reactions starting from phenols, o-, m-, p-cresols or ⁇ - or ⁇ -naphthols, particularly preferably in the synthesis of bisphenols, and most particularly preferably in the synthesis of BPA from phenol and acetone.
  • the preconditioned ion-exchange resin suspensions are however also outstandingly suitable for use as catalysts in addition reactions.
  • addition reactions are the addition of alcohols to alkenes, preferably of alcohols to C 1 -C 4 -alkenes, particularly preferably the addition of methanol, ethanol, propanol or butanol to isobutene, and most particularly preferably of methanol to isobutene to form methyl tert.-butyl ether.
  • the preconditioned ion-exchange resin suspensions are in addition suitable for the catalysis of esterifications by reaction of alcohols with carboxylic acids, preferably C 1 -C 8 -alcohols with C 1 -C 8 -carboxylic acids, particularly preferably for the esterification of methanol, ethanol, propanol and all isomers of butanol with carboxylic acids of the series formic acid, acetic acid, propionic acid or butyric acid.
  • preconditioned ion-exchange resin suspensions are suitable for the catalysis of transesterification reactions, for example of tri-esters to mono-esters, in particular the transesterification of a triglyceride with methanol, ethanol, propanol or butanol to a fatty acid mono-ester.
  • the conditioned ion-exchange resin suspensions are suitable for the catalysis of alkylation reactions, for example the alkylation of phenols or cresols with linear or branched olefins, for example to triisobutene or nonene.
  • the water wash (oxygen content in the fully deionized water ⁇ 20 ppb) is carried out in an intermittently stirred conditioning vessel under a nitrogen atmosphere in 12 cycles at 30° C., the residual conductivity of the wash water at the outlet being 14 microSiemens/cm in the last cycle.
  • the dewatering is carried out continuously under a nitrogen atmosphere at 70° C. with phenol. At the same time the volume of the ion exchanger decreases by ca. 48%.
  • the aqueous phenol occurring at the outlet is distilled off by distillation at initially 700 mbar and 105° C. bottom temperature. At the end of the distillation the vacuum is reduced to 130 mbar; the bottom temperature rises to 125° C.
  • the ion-exchange resin suspension preconditioned in this way is transported by means of conventional transportation means by rail and water to the desired production site.
  • the overall transport time is ca. 6 weeks.
  • the solidified ion-exchange resin suspension is melted for its transfer to the production vessel (reactor).
  • the partly heatable transporting container is heated with water at 75° C. and low pressure steam at a temperature of 110° C. In this connection care is taken to ensure that the temperature in the partly heatable railway wagon does not exceed 75° C. at any point.
  • the suspension After the suspension has been melted it is pumped by means of membrane pumps and addition of phenol, heated to a temperature of 70° C., from the transporting container to the reactor, and used for the continuous production of 2,2-bis(4-hydroxyphenyl) propane.
  • the phenol used for the pumping operations is purified by distillation at 120° C. and 150 mbar over sodium hydroxide (0.001 wt. %) and re-used in the process.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
US12/129,851 2007-06-08 2008-05-30 Method for decanting preconditioned ion-exchange resin suspensions Expired - Fee Related US8133928B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007026549 2007-06-08
DE102007026549.4 2007-06-08
DE102007026549A DE102007026549A1 (de) 2007-06-08 2007-06-08 Verfahren zum Umfüllen von vorkonditionierten Ionenaustauscherharz-Suspensionen

Publications (2)

Publication Number Publication Date
US20080306174A1 US20080306174A1 (en) 2008-12-11
US8133928B2 true US8133928B2 (en) 2012-03-13

Family

ID=39615772

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/129,851 Expired - Fee Related US8133928B2 (en) 2007-06-08 2008-05-30 Method for decanting preconditioned ion-exchange resin suspensions

Country Status (9)

Country Link
US (1) US8133928B2 (zh)
EP (1) EP2014363A3 (zh)
JP (1) JP5274113B2 (zh)
KR (1) KR20080108033A (zh)
CN (1) CN101318147B (zh)
DE (1) DE102007026549A1 (zh)
RU (1) RU2008122541A (zh)
SG (1) SG148924A1 (zh)
TW (1) TWI450763B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011086907A1 (de) 2010-12-23 2012-06-28 Schaeffler Technologies Gmbh & Co. Kg Vorrichtung zum Ausgleich von Drehmomentschwankungen
GB201701576D0 (en) * 2017-01-31 2017-03-15 Ge Healthcare Bio Sciences Ab Method and system for transferring separation resin
CN112718020B (zh) * 2020-12-18 2021-07-23 山东聚优新材料科技有限公司 一种阴离子交换树脂中间体氯球的安全运输与存储方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037052A (en) 1959-04-29 1962-05-29 Rohm & Haas Catalyzing reactions with cation exchange resin
GB967476A (en) 1961-05-05 1964-08-19 Shell Int Research Sulpholene purification process
US3284419A (en) 1961-03-23 1966-11-08 Shell Oil Co Poly
US4191843A (en) 1977-11-09 1980-03-04 Shell Oil Company Preparation of bisphenols
JPH06296871A (ja) 1993-04-20 1994-10-25 Chiyoda Corp 反応器に対するビスフェノールａ製造用触媒の充填方法
JPH06304479A (ja) 1993-04-20 1994-11-01 Chiyoda Corp 反応器に対するビスフェノールａ製造用触媒の充填方法
GB2336159A (en) 1998-04-08 1999-10-13 Bp Chem Int Ltd Resin composition for purification of carboxylic acids and/or carboxylic anhydrides
WO2001037992A1 (de) 1999-11-23 2001-05-31 Bayer Aktiengesellschaft Verfahren zur konditionierung von ionenaustauschern
US20030211934A1 (en) 2000-12-07 2003-11-13 Mitsubishi Chemical Corporation Method of preserving sulfonic acid-type cation-exchange resin modified with thiol-containing amine compound

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3077479A (en) * 1961-05-05 1963-02-12 Shell Oil Co Purification of sulfolene
JP2002292285A (ja) * 2001-03-30 2002-10-08 Nippon Shokubai Co Ltd アルキレンオキシドの付加反応用樹脂触媒の保存方法とその利用
KR20070102691A (ko) * 2005-01-28 2007-10-19 다우 글로벌 테크놀로지스 인크. 산 촉매로서 사용하기 전에 양이온 교환 수지를안정화시키는 방법, 및 화학 공정에서의 이러한 안정화된양이온 교환 수지의 용도
DE102005025788A1 (de) * 2005-06-04 2006-12-07 Bayer Materialscience Ag Verfahren zur Herstellung von hochreinem Bisphenol A

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3037052A (en) 1959-04-29 1962-05-29 Rohm & Haas Catalyzing reactions with cation exchange resin
US3284419A (en) 1961-03-23 1966-11-08 Shell Oil Co Poly
GB967476A (en) 1961-05-05 1964-08-19 Shell Int Research Sulpholene purification process
US4191843A (en) 1977-11-09 1980-03-04 Shell Oil Company Preparation of bisphenols
JPH06296871A (ja) 1993-04-20 1994-10-25 Chiyoda Corp 反応器に対するビスフェノールａ製造用触媒の充填方法
JPH06304479A (ja) 1993-04-20 1994-11-01 Chiyoda Corp 反応器に対するビスフェノールａ製造用触媒の充填方法
GB2336159A (en) 1998-04-08 1999-10-13 Bp Chem Int Ltd Resin composition for purification of carboxylic acids and/or carboxylic anhydrides
WO2001037992A1 (de) 1999-11-23 2001-05-31 Bayer Aktiengesellschaft Verfahren zur konditionierung von ionenaustauschern
US6723881B1 (en) * 1999-11-23 2004-04-20 Bayer Aktiengesellschaft Method for conditioning ion exchangers
EP1239958B1 (de) 1999-11-23 2004-09-29 Bayer MaterialScience AG Verfahren zur konditionierung von ionenaustauschern
US20030211934A1 (en) 2000-12-07 2003-11-13 Mitsubishi Chemical Corporation Method of preserving sulfonic acid-type cation-exchange resin modified with thiol-containing amine compound

Also Published As

Publication number Publication date
CN101318147A (zh) 2008-12-10
JP5274113B2 (ja) 2013-08-28
TWI450763B (zh) 2014-09-01
JP2009039707A (ja) 2009-02-26
DE102007026549A1 (de) 2008-12-11
TW200916190A (en) 2009-04-16
US20080306174A1 (en) 2008-12-11
CN101318147B (zh) 2013-07-31
EP2014363A2 (de) 2009-01-14
RU2008122541A (ru) 2009-12-20
SG148924A1 (en) 2009-01-29
KR20080108033A (ko) 2008-12-11
EP2014363A3 (de) 2009-03-11

Similar Documents

Publication Publication Date Title
CN1073068C (zh) 以丙酮部分转化提高双酚a反应生产能力、品质和/或收率的方法
US8133928B2 (en) Method for decanting preconditioned ion-exchange resin suspensions
CN101337885B (zh) 连续酯化反应制备丙二醇甲醚醋酸酯的方法
CN101875626A (zh) 一种固定化负载酸催化剂合成n-苯基马来酰亚胺的方法
CZ284098B6 (cs) Způsob zlepšené přípravy esterů nenasycených karboxylových kyselin a zařízení k provádění tohoto způsobu
JPS61230744A (ja) 強酸性カチオン交換触媒の処理方法
US5723691A (en) Method for preparing ion-exchange resin for use as a catalyst in the synthesis of bisphenols
ES2228621T3 (es) Procedimiento para la fabricacion de bisfenol a.
US20050177006A1 (en) Catalytic process for preparing bisphenol A
KR100698424B1 (ko) 이온교환제의 컨디쇼닝 방법
CN101985418A (zh) 一种制备2－甲氧基－1－丙醇醋酸酯的方法
CN1501902A (zh) 制造多酚的助催化剂
KR20140095717A (ko) 비스페놀 a의 제조 장치
EP0062653B1 (en) Vinyl acetate purification process
JP4452058B2 (ja) ビスフェノールａ製造用変性触媒の調製方法
WO2014031019A1 (en) Method of transforming by-products in the process of synthesis of bisphenol a
WO2004094346A2 (en) Purification of solvents used for the purification of alkylene oxide
US20120220798A1 (en) Method for carboxylic acid esterification
JPS6296453A (ja) アミノ酸エステル化反応装置
JPH1077280A (ja) トリオキサンの製造方法およびトリオキサンの製造装置
WO2000053315A1 (fr) Procede de preparation d'un catalyseur destine a etre utilise pour produire du bisphenol
EP0815910B1 (en) Process for the removal of corrosive compounds from a fluid stream
CN103991653B (zh) 粗制丙烯腈罐
WO2005023424A1 (ja) ビスフェノールａ製造用変性触媒の調製方法
CN112479857A (zh) 一种低压低温甲醇羰基化制备乙酸的强化反应系统及工艺

Legal Events

Date Code Title Description
AS Assignment

Owner name: BAYER MATERIALSCIENCE AG, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALPS, ERNST-JOACHIM;BLASCHKE, ULRICH;MUENNICH, CHRISTIAN;AND OTHERS;REEL/FRAME:021184/0424;SIGNING DATES FROM 20080618 TO 20080620

Owner name: BAYER MATERIALSCIENCE AG, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALPS, ERNST-JOACHIM;BLASCHKE, ULRICH;MUENNICH, CHRISTIAN;AND OTHERS;SIGNING DATES FROM 20080618 TO 20080620;REEL/FRAME:021184/0424

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20160313